Fibers comprising acrylonitrile polymers containing aluminum and silicon oxides



FEBERS v(I@MPRIS1N6 ACRYLONITRILE POLY- MERS CONTAINING ALUMINUM .AND SHJL CON OXEDES John R. Caldwell, Kingsport,-Tenn.,assignor to Eastman Kodak Company, Rochester,,N. Y., acorporation of New Jersey No Drawing. Application April 7, 1954 Serial No.421,681

6 Claims. (Cl. 260-41) This invention relates to acrylonitrile polymer compositions and more particularly to acrylontirile polymer compositions, containing aluminum .and siliconyoxides in a colloidal state of dispersion, from whichshaped articles such as synthetic fibers having improved dyeingproperties can be formed.

An object of the invention is to provide acrylonitrile polymer fibers that have improved dyeing properties. Another object of the invention is to provide acrylonitrile polymer fibers having an improved ironing temperature or hot bar sticking temperature. A further object of the invention is to provide a method for incorporating colloidal aluminum and silicon oxides in acrylonitrile polymers. Another object of theinvention is to provide a. method for preparing acrylonitrile polymer fibers that contain colloidal aluminum and silicon oxides dispersed uniformly throughout the cross-section. Other objects will appear hereinafter.

In accordance with the present invention, these and other objects are attained by polymerizing acrylonitrile, alone or with other monomers, in an aqueous suspension of mixed aluminum and silicon oxides that have been freshly precipitated. Under the conditions ofpolymerization the oxides retain their colloidal form and surface activity to a large extent throughout the processes of isolating, dissolving, and spinning the polymer. "Fibers containing from 8 to 15% ofthe colloidal oxides can be dyed to dark shades by ordinary; procedures with cellulose acetate dyes, acid wool dyes, vat dyes, and some mordant dyes. Furthermore, the presence of the oxides raises the ironing temperature or hot bar sticking temperature of the fibers by to C.

I have also found that mixtures of colloidal aluminum and silicon oxides are valuable for use inaccordance with my invention. The ratio of the oxides employed may lie in the range of 40 to 90% A1 0 and the preferred-range is to 75% A1 0 From 5 to 25% and preferably 8 to 15% of the mixed oxides are used, based on the weight of the acrylonitrile polymer.

In order to have a suitableaffinity for dyes, it is important that the oxides be precipitated in a colloidal form that has a high degree of surface activity. This is accom plished by precipitating the oxides from relatively dilute solutions. The oxides are conveniently precipitated by mixing aqueous solutions of a water-soluble aluminum salt and sodium silicate. The pH is then adjusted to 'a value of about 4 to 7 by the addition of alkali or acid,- as required. The chloride, sulfate, nitrate, or acetate; of aluminum is suitable.

Polyacrylonitrile, or interpolymers of acrylonitrile with other monomers, may be employed in the process of my invention. Monomers that may be used inthe preparation of interpolymers include: methyl acrylate, methyl methacrylate, vinyl acetate, isopropenyl acetate, vinyl chloride, methallyl alcohol, itaconic esters, and allyl esters. A particularly valuable class ofsinterpolymers is derived from unsaturated amides as represented by: acrylamide, methacrylamide, N-methyl acrylamide, N,N-

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be employed in accordance with the invention.

Surface active agents such as fatty alcohol sulfates, aromatic sulfonates, sulfosuccinic esters, soaps, etc., may be used while forming the composition. Ethylene oxide condensation products are useful as dispersing agents.

Peroxide catalysts such as sodium 'persulfate, hydrogen peroxide, perborates, etc., are used. Regulators and promoters such as sodium bisu1fite,-dodecyl mercaptan, amyl mercaptan, etc., may be employed for the polymerization.

The polymer products containing the specified oxides separate from the reaction medium as granular precipitates that are readily filtered and washed.

The products are soluble in the usual acrylonitrile polymer solvents such as dimethylformamide, dimethyl acetamide, ethylene carbonate, 'gamma-butyrolactone, ethylene cyanohydrin, etc. The solutions are usually cloudy or turbid-because of the colloidal oxides. However, the particlesizeis so'small that the solutions can be filtered and spun by the ordinary'methods.

Various well-known- Wetand dry spinning methods can be employed with my -novel--spinning solutions. The wet -or'dry spinning 'methodsflescribed in Emmett V.

Martin, U. S. application -Ser. No. 159,089, filed April 29, 1950, now Patent 2,697,023 of December 14, 1954 for Improvement in'Spinning Acrylonit'rile also may be employed to spin the spinning compositions of the presentinvention; The resulting fibers have a high ten- :sile strength and improved elastic properties.

The following dyes are among those which can be employed to color the fibers of the present invention:

, index Acid wooldyes: number Brilliant Milling Blue BA 37 Brilliant Milling Red RA 487 Brilliant MillingaGreen B 667 .Brilliant Milling YelloW 6G 138 Fast Light Yellow R 636 Scarlet 4RA Xylene Milling Black B 304 Vat dyes:

Ponsol Jade Green 1101 Ponsol Navy Blue,RA 1100 Ponsol jRed BND; 1162 Ponsol Violet RRD 1104 Ponsol Yellow 3R s 45,2 Sulfanthrene Brown GR 121 Mordant dyes: 7

Omega Chrome Brown 2R v 98 Omega Chrome Dark Violet D 169 Omega Chrome Orange G 274 Omega Chrome Red .13 652 Omega Chrome Yellow 36 52 Omega Chrome Black F t 204 These cellulose acetatedyes, wool dyes, vat dyes, and mordant dyes may be applied to the fibers by the method shown in Diserens, Louis, Chemistry and Technology of Dyeing andPrinting, New'York, The Reinhold Corporation, vol. I (1948), vol. El (1951), translated from the second German edition.

The mixture is stirred at 50 C. for 16 hours. precipitated polymer is filtered, washed, and dried. It is ,soluble in dimethyl acetarnide, dimethyl formamide, gam- 3 r The present invention is further illustrated in the following examples:

Example 1.Four and one-half grams of 23.0 g. acrylonitrile 2.0 g. isopropenyl acetate 0.3 g. potassium persulfate 0.2 g; dodecyl mercaptan The ma-butyrolactone, and ethylene carbonate.

A spinning solution is prepared by dissolving 10 g. of the polymer in 60 cc. dimethylformamide. The solution is filtered and extruded through a multihole spinneret into a coagulating bath consisting of 75% water-25% dimethylformamide. The filaments are washed, dried, and drafted 600% at an elevated temperature. The yarn has a strength of 2.5 grams per denier and elongation of 2024%. It has an ironing temperature or hot barsticking temperature of 220-230 C.

The fibers can be dyed to dark shades with cellulose acetate dyes, acid wool dyes, and vat dyes mentioned herein.

Example 2.Six grams AlCl -6H O is dissolved in 300 cc. Water. A solution of 3 g. Na CO and 4 g. Na SiO -9H O in 50 cc. water is added with stirring. A gelatinous precipitate of A1 and Si0 is formed. The following materials are added to the suspension:

23.0 g. acrylonitrile 2.0 g. N-methyl methacrylamide 0.3 g. potassium persulfate 0.2 g. sodium bisulfite 0.3 g. dodecyl mercaptan 0.5 g. sulfonated mineral oil The mixture is stirred at 55-60 C. for 3 hours. The precipitated polymer isfiltered, washed, and dried. The yield is 26 g.

The polymer is soluble in dimethylformamide, dimethyl acetamide, and gamma-butyrolactone. A solution in butyrolactone is spun by extruding into a heated air cabinet. After drafting, the fibers have a strength of 2.5 to 3.0 grams per denier and an elongation of 20-26%. They dye to dark shades with cellulose acetate dyes, acid Wool dyes, and vat dyes. They have a hot bar sticking temperature of 230-240 C.

Example 3.--Six grams AlCl -6H O is dissolved in 300 cc. water. A solution of 3 g. Na CO and 4 g. Na SiO -9H O in 50 cc. water is added with stirring. A gelatinous precipitate of A1 0 and SiO is formed. The following materials are added to the suspension:

23.0 g. acrylonitrile 3.0 g. of N-isopropyl acrylamide 0.3 g. potassium persulfate 0.2 g. sodium bisulfite 0.3 g. dodecyl mercaptan 0.5 g. sulfonated mineral oil The The 4 wool dyes, and vat dyes. They have a hot bar sticking temperature of 230-240 C.

Example 4.Eight grams of Na SiO -9H O is dissolved in 300 cc. water. A solution of 3 g. AlCl -6H O in 50 cc. water is added. The pH of the solution is then adjusted to 4-6 by the addition of dilute hydrochloric acid. A colloidal precipitate of A1 0 and Si0 is formed. The following materials are added:

25.0 g. acrylonitrile 0.2 g. potassium persulfate 0.3 g. dodecyl mercaptan 0.5 g. sulfated fatty alcohol The mixture is stirred at 50-55 C. for 8 hours. product is filtered, Washed, and dried.

The polymer gives fibers that dye well with cellulose acetate dyes, acid wool dyes, and vat dyes.

Example 5.Twelve grams AlCl -6H O is dissolved in 350 cc. water. A solution of 4 g. Na SiO -9H O and 5 g. Na CO in 50 cc. water is added with stirring. The pH of the suspension is then adjusted to 4-6 by the addition of sodium carbonate solution. The following materials are added:

The

21.0 g. acrylonitrile 4.0 g. vinyl acetate 0.3 g. potassium persulfate 0.2 g. dodecyl mercaptan 0.4 g. fatty alcohol sulfate The mixture is stirred at 50-55 C. for 12 hours. The product gives fibers that dye well with cellulose acetate dyes, vat dyes, and acid wool dyes. The fibers stick to the hot bar at 200-210 C.

Example 6.-Twelve grams AlCl -6H O is dissolved in 350 cc. water. A solution of 4 g. Na SiO -9H O and 5 g. Na CO in 50 cc. water is added With stirring. The pH of the suspension is then adjusted to 4-6 by the addition of sodium carbonate solution. The following materials are added:

21.0 g. acrylonitrile 4.0 g. N,N-diethyl acrylamide 5 0.3 g. potassium persulfate 3 0.2 g. dodecyl mercaptan 0.4g. fatty alcohol sulfate The mixtureis stirred at 50-55 C. for 12 hours. The product gives fibers that dye well with cellulose acetate dyes, vat dyes, and acid wool dyes. The fibers stick to the 'hot bar'at ZOO-210 C.

My present invention represents a new approach to the problem of improving the dyeing properties of acrylonitrile polymer fibers. Previous methods have all been based on the use of organic modifiers employed in copolymers, graft polymers or mixtures. My present method depends upon inorganic modifiers which have a highly active surface with a large capacity for absorption. Furthermore, employing the aluminum and silicon oxides permit a considerable economic advantage over most compounds such as acrylamides.

I claim:

1. Fibers having improved dyeing and sticking characteristics made from an acyclic acrylonitrile polymer composition selected from the group consisting of acrylonitrile, N-methyl methacrylamide copolymer; acrylonitrile. N-isopropyl acrylamide copolymer; polyacrylonitrilc; acrylonitrile, vinyl acetate copolymer; and acrylonitrile, N,N-diethyl acrylamide copolymer and containing A1 0 and SiO in colloidal form in an amount Within the range 'of 8 to 15% by weight of the polymer the A1 0 being present in an amount of 50 to of the total oxide mixture.

'. 2. Fibers having improved dyeing and heat sticking characteristics made from an acrylonitrile N-methyl methacrylamide copolymer composition containing A1 0 5 of 8 to 15% by weight of the copolymer the A1 being present in an amount of 50 to 75% of the total oxide mixture.

3. Fibers having improved dyeing and heat sticking characteristics made from an acrylonitrile N-isopropyl acrylamide copolymer composition containing Al O and SiO in colloidal form in an amount within the range of 8 to 15 by weight of the copolymer the A1 0 being present in an amount of 50 to 75 of the total oxide mixture.

4. Fibers having improved dyeing and heat sticking characteristics made from polyacrylonitrile composition containing A1 0 and SiO in colloidal form in an amount within the range of 8 to 15% by weight of the copolymer the A1 0 being present in an amount of 50 to 75% of the total oxide mixture.

5. Fibers having improved dyeing and heat sticking.

6 polymer composition containing A1 0 and SiO: in colloidal form in an amount within the range of 8 to 15% by weight of the copolymer the A1 0 being present in an amount of to of the total oxide mixture.

6. Fibers having improved dyeing and heat sticking characteristics made from acrylonitrile N,N-diethyl acrylamide copolymer composition containing A1 0 and SiO in colloidal form in an amount within the range of 8 to 15% by weight of the copolymer the A1 0 being present 10 in an amount of 50 to 75 of the total oxide mixture.

References Cited in the file of this patent UNITED STATES PATENTS Seymour "Apr. 12, 1949 Great Britain July 16, 1952 

1. FIBERS HAVING IMPROVED DYEING AND STICKING CHARACTERISTICS MADE FROM AN ACYCLIC ACRYLONITRILE POLYMER COMPOSITION SELECTED FROM THE GROUP CONSISTING OF ACRYLONITRILE, N-METHYL METHACRYLAMIDE COPOLYMER; ACRYLONITRILE N-ISOPROPYL ACRYLAMIDE COPOLYMER; POLYACRYLONITRILE; ACRYLONITRILE, VINYL ACETATE COPOLYMER; AND ACRYLONITRILE, N,N-DIETHYL ACRYLAMIDE COPOLYMER AND CONTAINING AL2O3 AND SIO2 IN COLLOIDAL FORM IN AN AMOUNT WITHIN THE RANGE OF 8 TO 15% BY WEIGHT OF THE POLYMER THE AL2O3 BEING PRESENT IN AN AMOUNT OF 50 TO 75% OF THE TOTAL OXIDE MIXTURE. 